Activation of CO by Hydrogenated Magnesium(I) Dimers: Sterically Controlled Formation of Ethenediolate and Cyclopropanetriolate Complexes

被引：108

作者：

Lalrempuia, Ralte ^{[1
]}

Kefalidis, Christos E. ^{[2
,3
]}

Bonyhady, Simon J. ^{[1
]}

Schwarze, Benedikt ^{[1
]}

Maron, Laurent ^{[2
,3
]}

Stasch, Andreas ^{[1
]}

Jones, Cameron ^{[1
]}

机构：

[1] Monash Univ, Sch Chem, Melbourne, Vic 3800, Australia

[2] Univ Toulouse, F-31077 Toulouse, France

[3] CNRS, INSA, UPS, UMR 5215,LPCNO, F-31077 Toulouse, France

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2015年 / 137卷 / 28期

基金：

澳大利亚研究理事会;

关键词：

CARBON-MONOXIDE; SELECTIVE FORMATION; HYDRIDE; CHEMISTRY; HOMOLOGATION; MECHANISM; ADDUCT;

D O I：

10.1021/jacs.5b06439

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

This study details the formal hydrogenation of two magnesium(I) dimers {(Nacnac)Mg}(2) (Nacnac = [{(C6H3R2-2,6)NCMe}(2)CH](-); R = Pri ((Dip)Nacnac), Et ((Dep)Nacnac)) using 1,3-cyclohexadiene. These reactions afford the magnesium(II) hydride complexes, {(Nacnac)Mg(mu-H)}(2). Their reactions with excess CO are sterically controlled and lead cleanly to different C-C coupled products, viz. the ethenediolate complex, ((Dip)Nacnac)Mg{kappa(1)-O-[((Dip)Nacnac)Mg(kappa(2)-O,O-O2C2H2)]}, and the first cyclopropanetriolate complex of any metal, cis-{((Dep)Nacnac)Mg}(3){mu-C-3(H-3)O-3}. Computational studies imply the CO activation processes proceed via very similar mechanisms to those previously reported for related reactions involving f-block metal hydride compounds. This work highlights the potential magnesium compounds hold for use in the Fischer-Tropsch-like transformation of CO/H-2 mixtures to value added oxygenate products.

引用

页码：8944 / 8947

页数：4

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